Mechanistic aspects of hydrodeoxygenation of para-methylguaiacol

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Mechanistic aspects of hydrodeoxygenation of para-methylguaiacol over Rh/silica and Pt/silica Florent Bouxin, Xingguang Zhang, Iain Kings, Adam Fraser Lee, Mark John H. Simmons, Karen Wilson, and S. David Jackson Org. Process Res. Dev., Just Accepted Manuscript • DOI: 10.1021/acs.oprd.8b00211 • Publication Date (Web): 29 Aug 2018 Downloaded from http://pubs.acs.org on August 29, 2018

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Organic Process Research & Development

Mechanistic aspects of hydrodeoxygenation of para-methylguaiacol over Rh/silica and Pt/silica.

Florent P. Bouxina, Xingguang. Zhangb, Iain N. Kingsc, Adam F. Leeb , Mark J. H. Simmonsc, Karen Wilsonb, S. David. Jackson*a a

Centre for Catalysis Research, School of Chemistry, University of Glasgow, Glasgow G12 8QQ, Scotland b

c

School of Science, RMIT University, Melbourne VIC3001, Australia

School of Chemical Engineering, University of Birmingham, Birmingham B15 2TT, UK

* Author to whom all correspondence should be addressed [email protected]

1 ACS Paragon Plus Environment

Organic Process Research & Development 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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Abstract.

The mechanism of p-methylguaiacol (PMG) hydrodeoxygenation (HDO) has been examined over two Rh/silica catalysts and a Pt/silica catalyst at 300 °C and 4 barg hydrogen. Sequential conversion of PMG to 4-methyl catechol is followed by m- and p-cresol formation, and finally toluene production, although direct conversion of PMG to p-cresol is favoured over a commercial Rh/silica catalyst. Dehydroxylation and hydrogenation are shown to occur over metal functions, while demethylation and demethoxylation are favoured over the fumed silica support. A mechanistic pathway for PMG hydrodeoxygenation is proposed.

Keywords. Para-methylguaiacol; hydrodeoxygenation; rhodium; platinum; mechanism.



Introduction.

Hydrodeoxygenation (HDO) of bio-oils is an active research area in both catalysis and bioenergy,1,2 and offers one of the methodologies capable of upgrading bio-oils into a form suitable for blending with petroleum. Previously,3 we examined the deactivation of three catalysts for the HDO of paramethylguaiacol, a common component of pyrolytic bio-oils. The catalysts were 2.5 wt% Rh/silica supplied by Johnson Matthey (JM), an in-house prepared 2.5 wt% Rh/silica (A) and 1.55 wt% Pt/silica (A). All three catalysts exhibited an initial deactivation phase, although the Rh/silica (JM) achieved steady-state after ~6 h on-stream and maintained a constant activity over the subsequent test period. In contrast, the two in-house catalysts did not reach steady state within the testing timeframe, both Rh/silica (A) and Pt/silica (A) underwent continuous deactivation, albeit following different mechanisms.3 Here we focus on the reaction mechanisms over the different catalysts, and their response to deactivation. There are no other literature studies of p-methylguaiacol, however guaiacol has been the subject of several investigations. Mu et al4 studied guaiacol HDO over a Rh/C catalyst at 40 bar hydrogen and 250 °C in a batch reactor, reporting demethoxylation as the dominant process resulting in phenol as the main product (~35 % selectivity) at a modest conversion of ~13 %; other major products were cyclohexanone and cyclohexanol (~25 % selectivity). Gutierrez et al.5 examined rhodium and platinum on zirconia supports for guaiacol HDO, predominantly observing hydrogenated products at 100 °C, with some deoxygenation at 300 °C, although few details were provided. Platinum catalysts have been somewhat more researched and their HDO mechanism considered. A detailed reaction network for guaiacol conversion over Pt/alumina was uncovered by Gates and co-workers,6 wherein a wide product distribution was detected, reflecting HDO in competition with transalkylation and hydrogenolysis. In the course of our previous work it became apparent that demethylation, demethoxylation, and hydrogenation pathways were affected differently


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by catalyst deactivation and we were interested to put this into context mechanistically, and through the use of two metals and two silica supports, determine the active sites for each reaction.

Results and Discussion.

The three catalysts were tested for para-methylguaiacol HDO over an extended period of 32 h. As previously reported, the Rh/silica (JM) catalyst achieved a steady state within the timeframe of the testing, whereas Rh/silica (A) and the Pt/silica (A) both exhibited continuous deactivation resulting in significant selectivity variations between 1 h and 32 h on stream (Figures 1-3).

Rh/silica (JM) 60

Selectivity (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


50 1 h TOS 40

32 h TOS

30 20 10 0

Figure 1. Product distribution for p-Methylguaiacol HDO over Rh/silica (JM); 47 % and 34 % conversion after 1 h and 32 h time on stream respectively.



Rh/silica (A) 60

Selectivity (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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1 h TOS

50

32 h TOS

40 30 20 10 0

Figure 2. Product distribution for p-Methylguaiacol HDO over Rh/silica (A); 50 % and 26 % conversion after 1 h and 32 h time on stream respectively.


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Pt/silica (A) 60

Selectivity (%)

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1 h TOS

50

32 h TOS

40 30 20 10 0

Figure 3. Product distribution for p-Methylguaiacol HDO over Pt/silica (A): 70 % and 47 % conversion after 1 h and 32 h time on stream respectively.

In the early stages of the test Rh/silica (A) is selective to toluene (33 %) and para-cresol (30 %) but after 32 h time on stream the major products are 4-methylcatechol (41 %) and para-cresol (34 %). This is in marked contrast to Rh/silica (JM), where toluene selectivity (< 5 %) and 4-methylcatechol selectivity (< 10 %) are both low throughout the test. Pt/silica (A) displays a less pronounced switchover from meta- and para-cresol to 4-methylcatechol production.

Mechanistically, the results for both Rh catalysts reflect sequential hydrogenolysis reactions as shown in Scheme 1. As Rh/silica (A) deactivates, it loses hydrogenolysis/HDO activity, such that the demethylation product 4-methycatechol is increasingly favoured. This selectivity switching 7 ACS Paragon Plus Environment


mirrors the relative ArO-CH3 versus Ar-OCH3 bond strengths of ~381 kJ.mol-1 versus 419 kJ.mol-1 respectively. None of the catalysts promoted C-C bond scission and concomitant benzene generation, and only products of cresol hydrogenation (p- and m-methylcyclohexanone) were

Scheme 1. Mechanism of hydrogenolysis/HDO of PMG.

observed, but not methylcyclohexane. 3-Methylanisole was only formed as a minor product over Rh/silica (A), suggesting that dehydroxylation of PMG to 3-methylanisole (and subsequent demethylation to m-cresol) is generally an unfavourable pathway consistent with its high energy barrier of ~431 kJ.mol-1. Demethylation of PMG to 4-methylcatechol was unaffected by deactivation, presumably reflecting the weaker bonds to be cleaved. p-Cresol may form by either direct demethoxylation of PMG, or (very energetically unfavourable) dehydroxylation of 4methylcatechol. Since p-cresol production was largely unaffected by deactivation, we conclude it forms through the former (less energy intensive) direct demethoxylation. Rh/silica (JM) is never effective for complete PMG dehydroxylation (toluene selectivity

Mechanistic aspects of hydrodeoxygenation of para-methylguaiacol

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